Alkylation process and catalyst therefor



. ride-form isoparafllns.

welll precede the alkylation noted by these inves'- Patented Apr. 6, 1943 UNITED STATES PATENT OFFICE THEREFOR ALKYLATIONPROOEQSSANDCATALYST Robert F. Rem-us, Chicago, 111.

Serial No. 383,803

. No Drawing. Application March 17, 1941,

is Claims.

invention relates to improved catalysts and processes for the alkylationof organic com- More specifically,this invention relates to improved catalystsf and processes for the alkylation of organic compounds with oleilnes. More particularly, this invention relates to improved catalysts and processes for the alkylatlon of hydrocarbons by oleilnes.

The alkylation of organic compounds i a'reac tion, well known in the art. For example, the

formationuof p-tertiary, butyl phenol by the alhydration of phenol with tertiarybutanol, tertiary butyl chloride, isobutylene, or similar reagentsin the, presence of suitable catalysts is well known in the 'art. Similarly, certain hydrocarbons, such asbenzene, toluene, naphthalene and the likeare easilynllqrlated with alkyl halides, alcohols, oleflnes} or similarreagents in the presence of suitable catalysts, the aluminum halides orconcentrated sulfuric acid being commonly used for the.

purpose.

More recently it hasbeen found that under certain conditions, paraillnic hydrocarbons may be directly alkylated with oleilnes, For example,

in my United States application, Serial Number 739,281, filed August 10,1934, which has since matured into United States Patent 2,082,518, issued 'Junefl, 1937. it is shown that when propylene-propane mixturesare passed over mercuric aluminum bromide, or antimonous aluminum bromide at750 pounds per squareinch pressure and temperatures of 100 to 200 F., the liquid polymer yield" is appreciably larger than the amount of propylene disappearing. Similarly, Ipatieil' and Groose (Journal of the American Chemical Society, volume 57, page-1616, 1935), showed that isoparafllns are alkylated with oleilnes in the presence of boron fluoride promoted with nickel powder and water (orhydrogen fluoride). Subsequently, Ipatiefr, Grosse, Pine and Komarewsky (ibid. volume 58, page 913, 1936). showed that aluminum chloride is a more general catalyst, both normal and isoparailins being alkylated with oleflnes inthe presence of this agent. In this connection referencemay be made to my United States application, Serial Number 32,379,1il'ed Julyf20, 1935,which has since matured, into. United States Patent 2,172,146, issued September 5, 1939, wherein it is shown that normal paraillns, in the presence of aluminum chlo- This isomerization may tigators. Other investigators have found that the alkylation, of paraflln hydrocarbons with olefines is catalyzed by such materials as lithium aluminum chloride, sodium aluminum chloride, and various aluminum halide-hydrocarbon complexes. More recently, it has been found that ordinary concentrated sulfuric acid is an excellent agent for catalyzing the alkylation of isoparaifins with olefines. For further information reference may be had to the article by Birch, Dunstan, Fidler, Pim and Tait in the Journal of the Institution of Petroleum Technologists, volume 24, page 303,

'for catalytic polymerization contain, in addition to isobutane and normal butane, isobutene, butene-1 and butene-2. During catalytic polymerization, the isobutene reacts rapidly, the normal butenes at a much' slower rate, so that by proper control of conditions it is possible to obtain practically quantitative conversion of isobutene together with normal butene conversions varying from practically zero up to practically 100%. The resulting polymer consists largely of isomeric octenes and has an octane number of to 82. This material is totally unsuited for use as an aviation fuel, due to the high unsaturate content, low octane number, and poor lead response. By hydrogenation, however, the

isomeric octenes are converted to isomeric octanes. The hydrogenated product contains no unsaturates, has an octane'number. of from to 98 or even higher, and exhibits an excellent lead response, and hence is well suited for use as an aviation-fuel. The octane number of the hydrogenatedproduct is largely a, function of the amount of normal butenes converted; when normal butene conversion is low octane number is high and vice versa.

It will be obvious to those skilled ,in the art 1 that alkylation offers many advantages over catalytic polymerization. By'the alkylation of isobutane with a normal butene or isobutene, an isomeric octane is formed directly and accordin ly the hydrogenation step, essential in the preparation of aviation fuels by catalytic polymerization, may be omitted. Furthermore, while in catalytic polymerization the maximum polymer yield can be no greater than the olefines present in the charge, in alkylation not only the olefines but also the isoparafflns react. Additionally, in alkylation there is no perceptible. difference between isobutene and the normal butenes, the oc tane numberof the alkylate being the same re- The alkylation of isoparafiins by oleflnes in the presence of sulfuric acid is a very simple process. A mixture of the two reactants, with the isoparafiln preferably in large excess, is contacted under vigorous agitation with concentrated sulfuric acid at low temperatures and atmospheric or slightly elevated pressures. The reaction product is separated, the alkylate being sent to storage while-the unreacted isoparafl'lns are mixed with fresh feed andrecycled to the reaction-zone. Ordinary room temperatures, or even lower temperatures, are commonly employed, for example, temperatures of 70 F. or below. such as 55 F.. 35 F., F., or even lower.

Theoretically.in the alkylation of isoparaffins with olefines, the sulfuric acid catalyst should remain unchanged indefinitely. Actually, however. the sulfuric acid, due to side reactions and to other causes, deteriorates more or lessranidly and must be replaced; In commercial operations it is common practice to withdraw acid from the alkylation reactor at a constant predetermined rate and replace that withdrawn with new acid at the same rate. The acid ,withdrawn has been The kylating at high temperatures, for example, 70 F. or more, it is preferable to remove 3 to 5 pounds or more of acid per gallon of alkylate formed. At lower temperatures, for example, F. or below, the acid may be removed at a rate of about one pound per gallon of alkylate formed. While operating at low temperatures reduces appreciably the amount of acid that must be restored, even one pound of acid per gallon of alkylate is equivalent to over '50 tons of acid per day for a plant producing 2500 barrels of alkylate, so that acid restoration remains a real problem.

- In addition, when operating at low temperatures found to contain water, sulfonic acids. sulfonates,

and similar products. so that while fresh 98% sulfuric acid is charged to the reactor. that withdrawn mav contain only 80 to 90% sulfuric acid and from 5 to 15%. more or less. of carbon. In the formation of traces of sulfonic acids. sulfonates and the like. traces of waterare produced simultaneously. thereby d lutin the acid. In addition, the feed commonly contains traces of water. which is also taken u be the acid. It has been found that for the alkvlatlon reaction to proceed at a reasonable rate the acid concentration should preferably be 90% or more and in no case less than 80%. Accordingly, it is obvious that the alkvlation acid must be restored to its initial strength from time totime by removal of the water formed in b g-reactions and taken u fr m the feed. Also. it has been found that used alkylation acid. after being restored to 98% strength. for example bv, the addition of sulfur trioxide. is not nearly as effective in catalyzing the reaction as new 98% acid. In other words. the organic matter in used alkylation acid exhibits an inhibiting effect on the reaction so that to re tore alkylation acid the organic matter as well as the water must be removed.

The amount of acid that must be continuously removed from the reactor and replaced by fresh in order to maintain a high catalyst efficiency varies with the reaction temperature. When althe rate of alkylation is low.

One object of this inventionis to provide improved sulfuric acid catalysts for the alkylation of organic'compounds. Furthermore, an object of this invention is toprovide sulfuric acid catalysts for the alkylation of organic compounds, said catalysts exhibiting high activity at low temperatures. An additional object of this invention is to provide sulfuric acid catalysts for the alkylation of organic compounds, said catalysts being easily restored after partial or complete exhaustion. Other objects of thisinvention will become evident from the accompanying description. e

In an attempt to increase the activity of sulfuric acid as a catalyst in the alkylation of isoparafllns with olefines, experiments were run in which the acid was promoted with small amounts of heavy metalsalts and mixtures thereof, for

example, salts of metals having an atomic number above 25 and a specific gravity of about 7.0 and mixtures of salts of such metals. Such promoted acids were more effective than the unpromoted acid in .catalyzing the alkylation of isoparaffins with olefines, some of the promoted acids being appreciably more effective than others. The most effective heavy metal salts for promoting the sulfuric acid catalyst were salts of metals having a 'specificgravity above 7.0 and falling in the first, second and eighth, groups of the periodic table, namely, salts of iron,

cobalt. nickel. copper. zinc, ruthenium,rhodium,

palladium, silver, cadmium, osmium, iridium platinum. gold and mercury.

Obviously, a large number of metals in'the g above list can be eliminated frompractical con-f sideration because of excessive cost. On the basis of the two criteria. cost and effectiveness, salts of nickel. copper. silver and mercury "appear to be the most suitable, although cadmium and zinc alsohave a high rating. Iron was found to be the least effective of the heavy metals listed.

When the concentrated sulfuric acid alkylation reduces acid consumption as has previously been pointed out. The increase in reaction rate is not at all surprising for in analytical chemistry it has long been known that the rate of olefine ab- "sorption from a gas sample can be increased by promoting the acid absorbent with a salt of copper. silver, mercury, nickel, etcetera or a mixture of salts of these metals. For further information on this point reference may be had to an article by Tropsch and Mattox, Industrial and v ,um, (added as selenious acid) and about 1.0% cop-' Engineering Chemistry, analytical edition, volume 6. page 404; 1935. Probably as acorollary of the increased reaction rate previously mentioned, ethylene acts as an alkylating agent to agreater extentthan in the presence of unprcmotedaci'd.

Additionally, the alkylation reaction is more clean cut in the presence oipromoted acid in that polymerisation of olefines is greatly curtailed, thusresultingin a more 'nearly saturated alkylate. Also, with unpromoted acid, a considerable part e of the appreciable polymer productlon dissolves in the acid and "thus contaminates it. As a 1 possible corollary of the repression of polymeriza tion, under otherwise similar conditions 'theyield oi' alkylate per pound of catalyst exhausted is .much higher if a 1 promoted catalyst is employed.

Further investigation has shown that the pro-f moting activity of heavy metal salts or mixtures thereof can be enhanced by the addition ofa selenium compound to the promoted acid. j Fur- 2o thermore, the presence of the selenium compound 1 is of greatest value in the restoration of promoted alkylation' acid; when I j exhausted, 'this catalytic activity of the selenium compoundin turn being enhanced by the heavy metalsalt' onsalts.

Carbon compoundsare removed from partially or completely exhausted unpromoted 1 acid by a very complicated procedure. This involvesthe' dilution of the partially or completely exhausted acid with water until the acid content is in the neighborhood or 50%. followed by cookingat temperatures somewhat" above the normal boiling point of water, for example, 220 to 240 F.. to hydrolyze and separate organic matter. By this" process most of the organic matterforms a-separate layer which canlbe skimmed fromthe dilute acid. Further reduction'in carbon content can be i accomplished by autoclaving the ly purified acid at temperatures some 100211. 1

' above those employedin" the cookingprocess and y 40 resulting'partial again removing the organic layer; Theresuiting dilute acid is concentrated as usual to say 93% strength and is then fortified to 98% strength'by I the addition of sulfur trioxide or oleuml In distinction to unpromoted sulfuric acid, it has been found that sulfuric acid, when promoted with a selenium compound and a small amount of a heavymetal salt or a mixture of heavy metal salts can, after partial or complete exhaustion be easily rendered carbon-free by simple heatinggfio On heating, the carboncompoundsin the doublv. promoted acid are readilyoxidiz edand eliminated as carbon dioxide, which is accompanied bysulfur dioxide. The resultingcarbon free acid can then be fortified with sulfur trioxide or oleum and 5 .To further aid in the understanding of my invention. the following examples are given. but it is tobeunderstood that these examples are il ustrative only and in no way limit the scope of the co invention.

1 Example 1 shame consisting of three volumesof isobutane and one volume isobutene was continuoualy passed with agitation through 9a% sulfuric "1' acid containing 0.10 to 0.15%byweight of seleni Der (added as copper oxide) The temperature wl-smalntained at 30 1'. After equilibrium had been shed, acid -was continuously it drawn from the reactor ata rate of 0.8 pound per gallon of alkylate formed while restored 98% acid (from a source to be described hereinafter) was addedto the -eactorat thesamerate. Theacid 7s extremely small.

rated with nickelfsulfate lowed by the slow addition selenium (added as dioxide) 3 withdrawn from the reactor. was heated to a temperature in the neighborhoodof 330 1". and was maintained at thistemperaturefor 15 minutes, Yollowing which the remaining liquid was fortifled withsufllcient oleum to give one pound of 98 acid per pound of acid withdrawn from there: actor and thethus' restored acid was returned to the. reactor at the same, rate as partially .eX- hausted I acid {was .withdrawn therefrom; The gases evolved during theheating of the acidwith; drawn from the reactor were treated in) manner well known in the art to convert the sulfur dioxide' component into sulfur trioxide and this inturn intooleum. It isobvious' that by thismethod or operation the loss of copper and selenium is nil or practicallyso while the" loss of sulfuricacid is i Example 2 One volume of concentrated'sulfuric acidsat ucentrated sulfuric "acid'containing 0.6% silversulfate were mixed." About10.1 the mixture, was added in the A gasstream consisting largely of isobutane was added tothe trebly promoted acid at 35 F. folof a gasmixture containing 35% butenes and35% propene. Reaction occurred under violent agitation and slight pressure; The alkylate yield was 181% based on the olefines consumed. The alkylafe was practically olefine free. The acid remaining at the end of this batch experiment was heated to 330 F. 'lhe small amount of carbon and carbon aceous materials therein wasrapidly oxidized. 15 5 7 3 1 Like Example-2, except that'the catalyst mixture consistedo'f concentrated sulfuric acid saturated: with nickel sulfate and experimental error the results could not be distinguishedfrom. those of therate of oleflne reaction was estimated to be 10% slower. :Exaniple 4 Like Example 2, ture consisted of concentrated sulfuric taining 0.6% silver sulfate and 0.1%. (added as dioxide).

acid "con- Withinthe limits of experimental error the results could not be distinguished from those obtained in Example 2.

Examples 5, 6,

Exactly like Emma 2, 3 and 4, except that the sulfuric acidalsocontained 1% mercury (added as oxide) in addition to the; other promoters named.

in some cases thereactionseemed tobeslightly more rapid in the presence of the mercury compound. However, it was definitely determined that the restoration of the partially spentcataiyst proceeded much more quickly in experiments in which the ,mercury compound was present. a

. As faras oxidation ofrcarbon compounds is concerned, it isbelieved thatthe selenium compound acts as an oxygencarrier between the sui-. furic acid and the carbon co'mpoundperhaps in accordance with the followingreactions:

The presence of mercuric sulfate evidently pros In its absence, ncselenic mote reaction "(1).

and 15 volumes of con-U selenium, based on form ofthe dioxide.

containing 0.1% Within the limit of Example 2 except that slightly slower,

except'that the catalyst mixselenium The alkylation reaction proceeded substa'ntially as in Examples 2, 3, and 4 except that,

' acid can be detected in the reaction mixture while these speculations are theory only and in no way limit the scope of the instant invention.

In the above examples the amounts of selenium and heavy metal given are indicative onlybut represent satisfactory proportions to employ under average conditions. It'should be understood that greater or lesser amounts may be employed as conditions dictate without departing from the spirit or scope of this invention. Since most heavy metal salts are but sparingly soluble in concentrated sulfuric acid, saturated solutions thereof with an excess of the salt in suspension may be employed if desired.

I As will be evident tothose skilled in the art, the exact form in whichv selenium and heavy metal are added to the, acidis .a matter of no great moment. They may be added as the elements, as a compound in the lower state of oxidation or as compound in the higher state of oxidation. assuming that two or more states of oxide tion exist of course, for regardless of the form added, the agent will rapidly achieve the proper state of oxidation. Metallic selenium, for example, apparently is peptized by sulfuric acid, giving a green colloidal solution which slowly becomes colorless (rapidly on heating) with the formation of selenious acid. 7 In the presenceof certain metal salts, particularly salts of mercury, this selenious acid becomes selenic acid when the mixture is heated. With respect to heavy metal salts, if these themselves are employed in making the catalyst, the exact nature of theanion' appears to b of no momentbut for obviousreasons the use of the sulfate is logical, albeit not necessary. Heavy metal selenites or selenates may be used to promote sulfuric acid for the purposes of this invention, for example, natural selenites of copthe destruction or organic by-products by oxidaper, cobalt and lead, artificial heavy metal selenites and selenates as well as doubleselenites and selenates such as NazHg(SeO )z and the like. While the present invention has been described largely in connection with the alkylation of isoparaillns with olefines, it is obvious that the in- I vention is of much wider scope, being applicable to practically any alkylation reaction wherein an organic compound is alkylated with an olefine or a material behaving as an oleiine, in the presence of concentrated sulfuric acid. For example, the teachings of this invention may be applied with success to the alkylation of cyclic hydrocarbons, such as benzene, toluene, cyclohexane, naphthalene and thelike, with oleflnes inthe presence of concentrated sulfuric acid. Also, this invention action destroys the activity of the acid before 1 any appreciable amount of organic contamination of the acid is observed. However, in such reactions the alkylation itself is promoted.

The teachings of this invention have also been applied to reactions which are not truly alkylation, for example, to the conversion of olefines to alcohols. In this process, oleflnes are reacted with sulfuric acid to form alkyl sulfates, the recompound.

tion. 1

This application is in part a continuation of my co-pending application, Serial Number 307,443,,filed December 4, 1939 Patent No. 2,295,- 608, issued September 15, 1942.

While the present invention has been described in connection with details or specific examples thereof, it is not intended that these shall be regarded as limitations upon the scope of this invention except insofar as included in the accompanying claims. I I

i I claim: Y

1. In the alkylation of isoparaflins with oleflnes, the improvement comprising employing a concentrated sulfuric acid catalyst containing a selenium. compound and a nickel compound.

2. In the alkylation of isoparaflinswith olefines, the improvement comprising employing a concentrated sulfuric acid catalyst containing a selenium compound and a copper compound.

3. In the alkylation of isoparamns with olefines, the improvement comprising employing a concentrated sulfuric acid catalyst containing a selenium compound and a silvercompound.

4. In the alkylation of isoparaflins with oleflnes, the improvement comprising employing a concentrated sulfuric acid catalystcontaining a selenium compound, a mercury compound anda nickel I compound.

5. In the alkylation ofisoparafiins with oleflnes,

the improvement comprising employing a con centrated sulfuric acid catalyst containing a selenium compound, a mercury compound and a copper compound.

6. In the alkylation of isoparafiins with olefines, the improvement comprising employing a concentrated sulfuric acid catalyst containing a selenium compound, a mercury compound and a silver compound. i

'7. An alkylation catalyst which comprises concentrated sulfuric'acid containing a selenium compound and a nickelcompound.

8. An alkylation catalyst which comprises concentrated sulfuric acid containing a selenium compound and a copper compound.

9. An alkylation catalyst which comprises concentrated sulfuric. acid containing a selenium compound and a silver compound.

, 10. An alkylation catalyst which comprises concentrated sulfuric acid containing a selenium compound, a mercury compound and a nickel compound.

11. An alkylation catalyst which comprises concentrated sulfuric acid containing a selenium compound, a mercury compound and a copper compound.

12. An alkylation catalyst which comprises concentrated sulfuric acid containing a selenium compound, a mercury compound, and a silver 13. In the alkylation of organic compounds, the improvement comprising employing a concentrated sulfuric acid catalyst containing a selenium compound and a compound of at least one metal selected from the group consisting of nickel, silver and copper.

14. In the alkylation of organic compounds, the

vimprovement comprising employing a concentrated sulfuric acid catalyst containing a selenium compound, a mercury'c'ompound and a compound of at least one metal selected from the group.

consisting of nickel, silver and copper.

, 15. In the alkylatlon oleiines, the improvement comprising employing a concentrated sulfuric acid catalyst containing a selenium compoundand-a compound or at least one metal selected from the group consisting of nickel, silver and copper.

16. In the alkylation of isoparafilns with oleflnes, the improvement comprising employing a concentrated sulfuric acid catalyst containing of isoparaflins with a selenium compound, a mercury compound and acompound of at least one metal selected from the group consistingof nickel, silver and copper.

17. An alkylation catalyst which comprises concentrated sulfuric acid containing a selenium compound and a compound of at least one metal selected from the group'consisting of nickel, silver ROBERT F. RU'IHRUFF. 

